U.S. patent number 10,479,845 [Application Number 15/500,941] was granted by the patent office on 2019-11-19 for process for preparing a halogenated elastomer with improved mooney viscosity stability.
This patent grant is currently assigned to ExxonMobil Chemical Patents Inc.. The grantee listed for this patent is ExxonMobil Chemical Patents Inc.. Invention is credited to John A. Clark, Stephen T. Dalpe, Leming Gu, Sunny Jacob, Mauritz Kelchtermans, Michael F. McDonald, Jr., Torri L. Rose.
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United States Patent |
10,479,845 |
Gu , et al. |
November 19, 2019 |
Process for preparing a halogenated elastomer with improved Mooney
viscosity stability
Abstract
This invention relates to a method of preparing a brominated
elastomer having a stabilized Mooney viscosity. The method includes
polymerizing isomonoolefins and at least one polymerizable unit to
obtain an elastomer/polymer; brominating the elastomer/polymer to
form a brominated elastomer effluent; neutralizing the brominated
elastomer effluent to form a neutralized effluent; volatizing off
the hydrocarbon solvent; and recovering a brominated elastomer. In
at least one point of the process, preferably prior to any
significant temperature change in the brominated polymer, a Mooney
stabilizer is added into the system. Portions of the Mooney
stabilizer may be added at multiple points into the process.
Inventors: |
Gu; Leming (Pearland, TX),
Dalpe; Stephen T. (Houston, TX), Kelchtermans; Mauritz
(Leefdaal, BE), Jacob; Sunny (Seabrook, TX),
Clark; John A. (Seabrook, TX), McDonald, Jr.; Michael F.
(Kingwood, TX), Rose; Torri L. (Humble, TX) |
Applicant: |
Name |
City |
State |
Country |
Type |
ExxonMobil Chemical Patents Inc. |
Baytown |
TX |
US |
|
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Assignee: |
ExxonMobil Chemical Patents
Inc. (Baytown, TX)
|
Family
ID: |
54325041 |
Appl.
No.: |
15/500,941 |
Filed: |
September 11, 2015 |
PCT
Filed: |
September 11, 2015 |
PCT No.: |
PCT/US2015/049641 |
371(c)(1),(2),(4) Date: |
February 01, 2017 |
PCT
Pub. No.: |
WO2016/053594 |
PCT
Pub. Date: |
April 07, 2016 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20170226238 A1 |
Aug 10, 2017 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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62057392 |
Sep 30, 2014 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08K
5/134 (20130101); C08K 5/3435 (20130101); C08K
5/13 (20130101); C08F 8/22 (20130101); C08F
8/22 (20130101); C08F 210/12 (20130101); C08K
5/13 (20130101); C08L 23/28 (20130101); C08K
5/134 (20130101); C08L 23/28 (20130101); C08K
5/3435 (20130101); C08L 23/28 (20130101); C08F
2810/50 (20130101); C08F 210/10 (20130101); C08F
236/08 (20130101) |
Current International
Class: |
C08F
8/22 (20060101); C08K 5/13 (20060101); C08K
5/134 (20060101); C08L 23/28 (20060101); C08F
236/08 (20060101); C08F 210/12 (20060101); C08F
210/10 (20060101); C08K 5/3435 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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105218719 |
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Jun 2017 |
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CN |
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2013/011017 |
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Jan 2013 |
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WO |
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2015/130391 |
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Sep 2015 |
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WO |
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2015/130392 |
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Sep 2015 |
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WO |
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Other References
Machine translated English language equivalent of CN 105218719
(Jun. 2017, 12 pages). cited by examiner .
Human translation of JP 01306443 (1989, 15 pages). cited by
examiner.
|
Primary Examiner: Johnston; Brieann R
Parent Case Text
PRIORITY CLAIM TO RELATED APPLICATIONS
This present application is a National Stage Application of
International Application No. PCT/US2015/049641 filed Sep. 11,
2015, which claims the benefit of and priority to U.S. Provisional
Application Ser. No. 62/057,392 filed Sep. 30, 2014, the
disclosures of which are is fully incorporated herein by their its
references.
Claims
What is claimed is:
1. A method of preparing a brominated elastomer, the method
comprising: (a) polymerizing a C.sub.4 to C.sub.7 isomonoolefin and
at least one monomer or other polymerizable unit to obtain a
C.sub.4 to C.sub.7 isomonoolefin derived elastomer; (b) adding a
first portion of a Mooney stabilizer to the C.sub.4 to C.sub.7
isomonoolefin derived elastomer; (c) contacting the C.sub.4 to
C.sub.7 isomonoolefin derived elastomer with a halogenating agent
and an emulsion in a bromination unit to form a brominated
elastomer effluent, wherein an optional portion of the Mooney
stabilizer is added to the bromination unit, wherein the emulsion
comprises an oxidizing agent, water, solvent, and surfactant; (d)
adding a portion of the Mooney stabilizer to the brominated
elastomer effluent; (e) neutralizing the brominated elastomer
effluent with a neutralizing agent and water to form a neutralized
effluent, wherein an optional portion of the Mooney stabilizer is
added to the neutralized effluent; (f) volatizing a hydrocarbon
solvent from the neutralizing effluent to form a brominated
elastomer slurry; (g) recovering a brominated elastomer from the
brominated elastomer slurry, wherein an optional portion of the
Mooney stabilizer is added to the recovered brominated
elastomer.
2. The method of claim 1, wherein the Mooney viscosity of the
recovered brominated elastomer does not increase by more than about
15 Mooney units when subject to 33.degree. C. for one year.
3. The method of claim 1, wherein greater than about 500 ppm of
Mooney stabilizer is added during the process of preparing the
brominated elastomer.
4. The method of claim 1, wherein the Mooney stabilizer is selected
from at least one of a sterically hindered nitroxyl ether,
sterically hindered nitroxyl radical, sterically hindered
phenolics, phosphites, and combinations thereof.
5. The method of claim 1, wherein the halogenating agent is
selected from at least one of molecular bromine, bromine chloride,
hydrogen bromide, and sodium bromide.
6. The method of claim 1, wherein the oxidizing agent is a material
which contains oxygen selected from at least one of a water soluble
oxygen containing agent, hydrogen peroxide, organic hydrogen
peroxide, sodium chlorate, sodium bromate, sodium hypochlorite,
sodium hypobromite, oxides of nitrogen, ozone, urea peroxidate,
pertitanic perzirconic, perchromic, permolybdic, pertungstic,
perunanic, perboric, perphosphoric, perpyrophosphoric, persulfates,
perchloric, perchlorate, and combinations thereof.
7. The method of claim 1, wherein the oxidizing agent is a water
soluble oxygen containing agent.
8. The method of claim 1, wherein the solvent is selected from at
least one of pentane, hexane, heptane, mono-, di-, or
tri-halogenated C.sub.1 to C.sub.6 paraffinic hydrocarbon, methyl
chloride, and combinations thereof.
9. The method of claim 1, wherein the bromination unit is a mixed
flow stirred tank, a conventional stirred tank, a packed tower, or
a pipe.
10. An article made from the brominated elastomer prepared by the
method of claim 1, wherein the article is a tire innerliner or a
tire bladder or is incorporated as a layer into a tire, a bladder,
a hose, a belt, pneumatic spring, or vehicle body mount.
Description
FIELD OF THE INVENTION
The present invention relates to a halogenated polymer having
improved Mooney viscosity stability and a method of obtaining such
a polymer. More particularly, the present invention is directed to
a method of producing a halogenated polymer using a halogen
regeneration process wherein the resulting polymer has improved
Mooney viscosity stability over time.
BACKGROUND OF THE INVENTION
The regenerative halogenation process is accomplished by contacting
a polymer, which has been dissolved in a solvent, a halogenating
agent, and an emulsion. The halogenating agent includes but is not
limited to molecular bromine, bromine chloride, hydrogen bromide,
sodium bromide, or a mixture thereof. The emulsion is a mixture of
a water soluble oxidizing agent capable of converting hydrogen
halide to a free halogen, an emulsifying agent, an organic solvent,
and water. The halogenated polymer is recovered from the mixture.
More information about known regenerative halogenation processes is
disclosed in U.S. Pat. Nos. 5,681,901 and 5,569,723.
While halogenated polymers manufactured using the regenerative
process yield a greater maximum theoretical halogenation
utilization compared to conventional halogenation methods, the
regenerative process results in increased levels of Mooney
viscosity growth of the polymers when compared with polymers
halogenated by the conventional methods. Mooney viscosity growth,
or Mooney growth, can lead to unsatisfactory processability of
compound formulations, such as innerliner formulations. Unlike
bromobutyl polymers, chlorobutyl polymers generally do not
experience the same degree of increasing Mooney viscosity as
bromobutyl polymers due to the greater bonding strength of chlorine
and the associated backbone carbon, as compared to bromine, to the
polymer structure. FIG. 3 shows the change in Mooney viscosity for
both conventionally produced bromobutyl and prior bromine
regenerative produced bromobutyl. As seen in FIG. 3, all bromobutyl
polymers undergo some degree of increase in the Mooney viscosity as
the polymer ages. For bromine regenerative produced bromobutyl, the
slope of the increase in Mooney viscosity is greater. For instance,
Mooney viscosity growth of polymers prepared by regeneration is
about twice that of polymers prepared by conventional methods
stored in warehouse conditions for about 2.5 years (approximated by
an Oven Aging Test described later herein). While a small increase
in polymer Mooney viscosity does not negatively alter the products
made using the polymer, or alter any manufacturing processes using
the polymer, accelerated Mooney viscosity growth reduces the shelf
life of the halogenated polymer.
U.S. Ser. No. 61/946,018, filed on Feb. 28, 2014, discloses adding
free radical scavengers to the final polymers produced by the
conventional and bromine regeneration processes to suppress the
Mooney viscosity growth. U.S. Ser. No. 61/946,035, filed on Feb.
28, 2014, discloses adding an ionomer stabilizer to the final
elastomeric nanocomposite to suppress the Mooney growth. There is
still a need to modify the regenerative halogenation process known
in the art whereby the resulting polymer has a reduced Mooney
viscosity growth.
SUMMARY OF THE INVENTION
The present invention is directed to a process for making an
elastomeric composition having improved characteristics over
previously known similar compositions.
This invention is directed to a method of preparing a brominated
elastomer. The method comprises polymerizing a C.sub.4 to C.sub.7
isomonoolefin and at least one monomer or other polymerizable unit
to obtain a C.sub.4 to C.sub.7 isomonoolefin derived elastomer;
contacting the C.sub.4 to C.sub.7 isomonoolefin derived elastomer
with a halogenating agent and an emulsion in a bromination unit to
form a brominated elastomer effluent; neutralizing the brominated
elastomer effluent with a neutralizing agent and water to form a
neutralized effluent; volatizing a hydrocarbon solvent from the
neutralized effluent to form a brominated elastomer slurry; and
recovering a brominated elastomer from the brominated elastomer
slurry. To suppress or reduce the Monney viscosity growth of the
recovered brominated elastomer, a Mooney stabilizer is added to the
process before the effluent or stream containing the brominated
elastomer undergoes a significant temperature change. The
stabilizer may be present during neutralization and should be in
present in the neutralized effluent so prior to volatizing of the
hydrocarbon solvent. Preferably, the recovered brominated elastomer
has a Mooney viscosity value that does not increase by more than 17
Mooney units for up to one year when stored at 33.degree. C. In
another embodiment, the recovered brominated elastomer has a Mooney
viscosity value that does not increase by more than 15 Mooney units
for up to one year when stored at 33.degree. C. In another
embodiment, the recovered brominated elastomer has a Mooney
viscosity value that does not increase by more than 11.5 Mooney
units for up to nine months when stored at 33.degree. C.
This invention is also directed to a method of preparing a
brominated elastomer, the method comprising polymerizing a C.sub.4
to C.sub.7 isomonoolefin and at least one additional polymerizable
monomer or unit, such as isoprene or alkylstyrene, to obtain a
C.sub.4 to C.sub.7 isomonoolefin derived elastomer; adding a first
portion of a Mooney stabilizer to the C.sub.4 to C.sub.7
isomonoolefin derived elastomer; contacting the C.sub.4 to C.sub.7
isomonoolefin derived elastomer with a halogenating agent and an
emulsion in a bromination unit to form a brominated elastomer
effluent, wherein an optional portion of the Mooney stabilizer is
added to the bromination unit; adding an optional portion of the
Mooney stabilizer to the brominated elastomer effluent;
neutralizing the brominated elastomer effluent with a neutralizing
agent and water to form a neutralized effluent, wherein an optional
portion of the Mooney stabilizer is added to the neutralized
effluent; volatizing a hydrocarbon solvent from the neutralizing
effluent to form a brominated elastomer slurry; recovering a
brominated elastomer from the brominated elastomer slurry, wherein
an optional portion of the Mooney stabilizer is added to the
brominated elastomer.
Furthermore, this invention is directed to a brominated elastomer
comprised from a C.sub.4 to C.sub.7 isomonoolefin and at least one
monomer or polymerizable unit to obtain a C.sub.4 to C.sub.7
isomonoolefin derived elastomer, the elastomer further having 0.001
to 0.2 mol % allylic alcohol, wherein the Mooney viscosity of the
brominated elastomer does not increase by more than about 15 Mooney
units for up to about 10 days at 80.degree. C. via an Oven Aging
Test or the Mooney viscosity of the brominated elastomer does not
increase by more than about 15 Mooney viscosity units for up to a
year when stored at 33.degree. C.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be described by way of example and with
reference to the accompanying drawings in which:
FIGS. 1 and 2 show the regenerative halogenation processes of the
invention.
FIG. 3 shows the Mooney viscosity growth of polymers produced by
conventional bromination and prior regenerative bromination
processes.
FIG. 4 shows the GPC Mz of polymers prepared by conventional
bromination and prior regenerative bromination processes at
different stages of the bromination process.
FIG. 5 shows the change in Mooney growth of polymers prepared by
conventional bromination and regenerative bromination
processes.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a regenerative halogenation
process wherein the resulting halogenated polymer experiences a
slower Mooney viscosity growth after a period of time. All
polymers, due to the active sites in the polymer structure,
experience occasional inter-chain coupling between the polymer
chains, whereby due to time and temperature the molecular weight
increases. This coupling produces larger polymer chains present in
the mass, which thereby increases the Mooney viscosity which is
related to molecular weight of the polymer mass, as seen in FIG. 3.
The coupling also affects the Z-average molecular weight (Mz) and
molecular weight distribution (MWD) due to the presence of the
newly created larger polymers.
As seen in FIG. 3, the increase in Mooney viscosity is greater for
brominated polymers prepared by known bromine regenerative
processes than for conventionally brominated polymers. The present
invention is directed to obtaining a halogenated polymer produced
using an improved regenerative halogenation process wherein the
polymer has a Mooney viscosity growth comparable to that of a
conventionally halogenated polymer.
Definitions
Definitions applicable to the presently described invention are as
described below.
Polymer may be used to refer to homopolymers, copolymers,
interpolymers, terpolymers, etc. Likewise, a copolymer may refer to
a polymer comprising at least two monomers, optionally with other
monomers. When a polymer is referred to as comprising a monomer,
the monomer is present in the polymer in the polymerized form of
the monomer or in the polymerized form of a derivative from the
monomer (i.e., a monomeric unit). However, for ease of reference
the phrase comprising the (respective) monomer or the like is used
as shorthand. Likewise, when catalyst components are described as
comprising neutral stable forms of the components, it is well
understood by one skilled in the art, that the ionic form of the
component is the form that reacts with the monomers to produce
polymers.
Elastomer refers to any polymer or blend of polymers consistent
with the ASTM D1566 definition: "a material that is capable of
recovering from large deformations, and can be, or already is,
modified to a state in which it is essentially insoluble, if
vulcanized, (but can swell) in a solvent." Elastomers are often
also referred to as rubbers; the term elastomer may be used herein
interchangeably with the term rubber. Preferred elastomers have a
melting point that cannot be measured by Differential Scanning
calorimetry (DSC) or if it can be measured by DSC is less than
40.degree. C., or preferably less than 20.degree. C., or less than
0.degree. C. Preferred elastomers have a Tg of -50.degree. C. or
less as measured by DSC.
Mooney viscosity or viscosity means the viscosity measure of
rubbers. It is defined as the shearing torque resisting rotation of
a cylindrical metal disk (or rotor) embedded in rubber within a
cylindrical cavity. The dimensions of the shearing disk viscometer,
test temperatures, and procedures for determining Mooney viscosity
are defined in ASTM D1646. Mooney viscosity is measured in Mooney
units and reported herein as ML 1+8 at 125.degree. C.
Isoolefin refers to any olefin monomer having at least one carbon
having two substitutions on that carbon. Multiolefin refers to any
monomer having two or more double bonds. In a preferred embodiment,
the multiolefin is any monomer comprising two conjugated double
bonds such as a conjugated diene like isoprene.
Isobutylene based elastomer or polymer refers to elastomers or
polymers comprising at least 70 mol % repeat units from
isobutylene.
Elastomer
Useful elastomeric polymers for this invention include elastomers
derived from a mixture of monomers, the mixture having at least (1)
a C.sub.4 to C.sub.7 isoolefin monomer component with (2) at least
one multiolefin or other polymerizable monomer component. The
isoolefin is present in a range from 70 to 99.5 wt % by weight of
the total monomers in any embodiment, or 85 to 99.5 wt % in any
embodiment. The multiolefin derived or other polymerizable monomer
component is present in amounts in the range of from 30 to about
0.5 wt % in any embodiment, or from 15 to 0.5 wt % in any
embodiment, or from 8 to 0.5 wt % in any embodiment.
The isoolefin is a C.sub.4 to C.sub.7 compound, non-limiting
examples of which are compounds such as isobutylene, isobutene,
2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-butene,
2-butene, methyl vinyl ether, indene, vinyltrimethylsilane, hexene,
and 4-methyl-1-pentene. The multiolefin is a C.sub.4 to C.sub.14
multiolefin such as isoprene, butadiene,
2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethyl-fulvene,
hexadiene, cyclopentadiene, and piperylene. Other polymerizable
monomers such as styrene and dichlorostyrene are also suitable for
homopolymerization or copolymerization in butyl rubbers.
Preferred elastomers useful in the practice of this invention
include isobutylene-based copolymers. As stated above, an
isobutylene based elastomer or a polymer refers to an elastomer or
a polymer comprising at least 70 mol % repeat units from
isobutylene and at least one other polymerizable unit. These
polymers are also conventionally referred to as butyl rubbers. One
butyl rubber polymer of the invention is obtained by reacting
isobutylene with 0.5 to 8 wt % isoprene, or reacting isobutylene
with 0.5 wt % to 5.0 wt % isoprene--the remaining weight percent of
the polymer being derived from isobutylene.
Other elastomeric polymers of the present invention are derived
from at least one random copolymer comprising a C.sub.4 to C.sub.7
isoolefin and an alkylstyrene comonomer. The isoolefin may be
selected from any of the above listed C.sub.4 to C.sub.7 isoolefin
monomers, and is preferably an isomonoolefin, and in any embodiment
may be isobutylene. The alkylstyrene may be para-methylstyrene,
containing at least 80%, more alternatively at least 90%,
preferably 95%, by weight of the para-isomer and can also include
functionalized terpolymers. The random copolymer has at least one
or more of the alkyl substituents groups present in the styrene
monomer units. In any embodiment, the elastomer comprises random
polymers of isobutylene and 0.5 to 20 mol % para-methylstyrene.
In any embodiment of the invention, other useful elastomers include
other unsaturated copolymers of isoolefins. Non-limiting examples
of such unsaturated polymers are poly(styrene-co-butadiene),
star-branched isobutylene-isoprene, star-branched
isobutylene-p-methylstyrene, isobutylene-isoprene-alkylstyrene
block polymers and random polymers of
isobutylene-isoprene-alkylstyrene.
The above polymers may be produced by any suitable means known in
the art, and the invention is not herein limited by the method of
producing the polymer. The polymers are traditionally produced in
either a slurry polymerization process or a solution polymerization
process. If the polymer is produced in a slurry polymerization
process whereby the polymer precipitates out of the reaction
medium, then the polymer is dissolved into a suitable solvent,
i.e., the creation of a polymer cement, prior to halogenation. For
polymers produced via a solution process, after removal of
unreacted monomers and removal or neutralization of unused
catalysts, the same polymer containing solution, or polymer cement,
may be used for halogenation. The polymer cement contains 1 to 70
wt % polymer, alternatively 10 to 60 wt % polymer, alternatively 10
to 50 wt % polymer, or alternatively 10 to 40 wt % polymer.
Method of Preparing Halogenated Elastomers
One method of preparing bromobutyl elastomers via bromine
regeneration is described in detail in U.S. Pat. No. 5,670,582.
Isobutylene based polymers having unsaturation in the polymer
backbone, such as isobutylene-isoprene polymers, may be readily
halogenated using an ionic mechanism during contact of the polymer
with a halogen source, e.g., molecular bromine or chlorine, and at
temperatures in the range of from about 20.degree. C. to 80.degree.
C. Isobutylene based polymers having no unsaturation in the polymer
backbone, such as isobutylene-alkylstyrene polymers, undergo
halogenation under free radical halogenation conditions, i.e., in
the presence of white actinic light or by inclusion of an organic
free radical initiator in the reaction mixture, and at temperatures
of 20.degree. C. to 90.degree. C.
As discussed above, conventional regenerative halogenation process
occurs by contacting a polymer solution with a halogenating agent
and an emulsion containing an oxidizing agent. The oxidizing agent
interacts with hydrogen halide created during halogenation,
converting the halogen back into a form useful for further
halogenation of the polymer thereby improving the halogen
utilization.
The regenerative bromination process 1 of the invention is
illustrated in FIG. 1. Polymer cement is fed per feedstream C into
a bromination unit 10. The bromination unit 10 may be any
conventional means permitting the desired reaction; it may be a
mixed flow stirred tank, a conventional stirred tank, a packed
tower, or a pipe with sufficient flow and residence time to permit
the desired reaction to occur. The halogenating agent, in the form
of molecular bromine, bromine chloride, hydrogen bromide, sodium
bromide, or a mixture thereof is fed per feedstream B into the
bromination unit 10.
An emulsion is fed per feedstream E into the bromination unit 10.
The emulsion is composed of the oxidizing agent, water, solvent,
and an emulsifying agent, such as a surfactant. The emulsion is
prepared by providing a 10 to 80 wt %, alternatively a 20 to 70 wt
% or 25 to 45 wt %, solution of the oxidizing agent in water and
mixing this with a solvent and an emulsifying agent under suitable
mixing conditions to form a stable emulsion. The emulsion may be
achieved by mixing the aqueous phase into the emulsifying agent
containing solvent, or by mixing the oxidizing agent with the
emulsifying agent first and then combining with the solvent. The
amount of oxidizing agent is in the range of 0.1 to 3,
alternatively 0.25 to 3, or alternatively 0.5 to 3 moles of active
oxidizing agent per mole of halogenating agent. Use of an oxidizing
agent during bromination increases bromine utilization to about 70
to 85%.
Oxidizing agents useful in the process are materials which contain
oxygen, preferably water soluble oxygen containing agents. Suitable
agents include peroxides and peroxide forming substances as
exemplified by the following substances: hydrogen peroxide, organic
hydrogen peroxide, sodium chlorate, sodium bromate, sodium
hypochlorite or bromite, oxygen, oxides of nitrogen, ozone, urea
peroxidate, acids such as pertitanic perzirconic, perchromic,
permolybdic, pertungstic, perunanic, perboric, perphosphoric,
perpyrophosphoric, persulfates, perchloric, perchlorate and
periodic acids. Of the foregoing, hydrogen peroxide and hydrogen
peroxide-forming compounds, e.g., per-acids and sodium peroxide,
have been found to be highly suitable for carrying out the desired
halogen regeneration.
The choice of solvent for the emulsion may be any solvent suitable
for use or used in forming the polymer cement; in one embodiment,
the solvent is selected to be the same solvent used to form the
polymer cement. Suitable solvents include hydrocarbons such as
pentane, hexane, heptane, and the like, inert halogen containing
hydrocarbons such as mono-, di-, or tri-halogenated C.sub.1 to
C.sub.6 paraffinic hydrocarbon or a halogenated aromatic
hydrocarbon such as methyl chloride, methylene chloride, ethyl
chloride, ethyl bromide, dichloroethane, n-butyl chloride, and
monochlorobenzene or mixtures of the hydrocarbon and inert
halo-hydrocarbon solvent. Furthermore, the solvent may be one
combination of the solvents provided herein, including isomers
thereof.
The emulsion via feedstream E may be introduced into the
bromination unit 10 at the beginning of the halogenation cycle or
after consumption of the bromine via halogenation of the polymer
has begun. The bromination reaction and the bromine regeneration
reaction occurs in the range of 20.degree. C. to 90.degree. C. for
a time sufficient to complete bromination of the polymer. When
molecular bromine is the halogenating agent introduced via feed
stream B, bromine consumption is indicated by a color change of the
reaction mixture from a reddish brown to a light tan or amber
color. Following sufficient reaction time in the bromination unit
10, the bromination effluent, stream F, exiting the bromination
unit 10, is neutralized by blending the effluent stream F with a
neutralization feed stream N, optionally comprising dilution water
W, in a neutralization unit 20. Heat is neither introduced nor
removed from the effluent F prior to neutralization and any change
in temperature of the stream is due to the heat of reaction of
neutralization. In an embodiment, heat may be introduced or removed
prior to neutralization.
Per prior known neutralization methods, the neutralized effluent
stream exiting the neutralization unit 20, NF, is sent to a slurry
(or flash) tank 30 to recover the polymer from the neutralized
effluent in which the now-brominated polymer remains dissolved
therein. In an embodiment, multiple slurry (or flash) tanks can be
present in this stage of the process and may be operated in series
or in parallel. Steam S, at temperatures from 120.degree. C. to
200.degree. C., preferably about 150.degree. C. to 180.degree. C.,
is introduced into the slurry tank 30 to volatize the hydrocarbon
solvents, the volatized solvent being removed by the overhead
stream O. Temperatures in the slurry tank 30 are in the range of
80.degree. C. to 200.degree. C., or alternatively in the range of
90.degree. C. to 120.degree. C. The temperature of the components
in the slurry tank 30, including the polymer in the formed slurry,
are dependent on the amount and temperature of the steam S mixed
with the neutralized effluent stream NF to achieve removal of the
hydrocarbon solvent. The polymer temperature will be in the range
of 100.degree. C. to 175.degree. C.
The slurry tank overhead stream O may be sent to a separator
wherein the volatized hydrocarbon solvent is separated from any
water contained in the overhead stream; the recovered hydrocarbon
solvent is preferably treated and recycled back into the
polymerization or bromination process. Water recovered from the
separator may be recycled back into the neutralization feed
stream.
Following removal of volatized solvent via overhead stream O, the
slurry tank effluent R is a slurry mixture of water and
precipitated brominated polymer, as well as residual components.
The polymer slurry R enters an extrusion drying unit 40 for removal
of the water and recovery of a polymer product stream P.
In an embodiment, additives known in the art, including but not
limited to epoxidized soybean oil (also referred to as ESBO) and
calcium stearate, may be added during the regenerative process.
ESBO may be added in the range of about 1 to about 2 phr in unit 40
during the drying step. Calcium stearate may be added to the cement
to the neutralization unit 20, and/or may be added to the slurry
tank 30 to help the polymer from sticking to the equipment and to
control the rubber particle size in the water slurry, and/or may be
added to unit 40 during the drying step. Referring to FIG. 1, in an
embodiment, antioxidants, such as Mooney stabilizers discussed
below, may be added to the extrusion drying unit 40 via X5.
An alternative embodiment of the regenerative bromination process 2
of the invention is illustrated in FIG. 2. After the cement is
neutralized in a neutralization unit 20, it is fed to a devolatizer
unit 50 where volatized solvent is removed by overhead stream O,
recovering polymer product stream P. In this embodiment, heat is
provided as input to the devolatizer 50 via mechanical energy
and/or surface heating via hot oil or any other heat transfer
medium. In an embodiment, ESBO may be added to unit 50 of FIG. 2
and calcium stearate may be added to unit 20 and/or unit 50 of FIG.
2. Referring to FIG. 2, in an embodiment, antioxidants, such as
Mooney stabilizers, may be added to the devolatizer unit 50 via
X6.
As discussed above and depicted in FIG. 3, polymers prepared by
bromine regenerative methods are susceptible to an increase in
Mooney growth when stored in warehouses. To aid in understanding
the accelerated Mooney viscosity growth, numerous samples were
taken at various points in a conventional bromination process and
in the known regenerative bromination process, sampling occurring
from post polymer formation to dry polymer baling.
The inventors have discovered that Mz, measured by Gel Permeation
Chromotography (GPC) methods known in the art, is useful for
predicting the future Mooney viscosity growth. Accordingly, by
measuring the change in Mz of a sample taken from the slurry tank
30 of FIG. 1 versus a sample taken from the neutralized cement NF,
it is possible to predict the Mooney viscosity growth of the sample
polymer after baling and packaging while aging in a warehouse. The
Mz at various sampling points in the conventional and regenerative
processes known in the art is shown in FIG. 4, corresponding to the
locations indicated in FIG. 1. While the polymer samples had
different Mooney viscosities, thus, the different initial Mz
values, the trend line of Mooney viscosity change (based on the
changed in GPC Mz) for the polymers formed by both processes are
informative. As evident from the sampling data of FIG. 4, the Mz
(and therefore the Mooney viscosity) of the conventionally
manufacturing brominated polymer, Conventional, is relatively
consistent through the process. The polymer undergoing bromination
via the known regenerative bromination process, Bromo Regen,
evidences a sharp increase in Mz after neutralization (labeled as
"NF") and during devolatization and precipitation of the polymer
into a slurry (labeled as "R"). The distinct process change at this
point is a change in temperature of the polymer, from a range of
20.degree. C. to 80.degree. C. to a range of 100.degree. C. to
120.degree. C. and the polymer is exposed to high temperature steam
used for volatizing/removing the hydrocarbon solvent.
While not wishing to be bound to a single theory for this molecular
weight/viscosity increase, Applicants believe during the
regenerative bromination process, the elastomer is also oxidized by
the oxidizing agent and its decomposition product of oxygen. The
oxidative structures are very low in concentrations; one known
resulting structure in the elastomer is allylic alcohol present in
an amount of 0.001 to 0.2 mol %. When the polymer is subjected to a
significant heat change, such as the slurry process following
neutralization, the oxidized structures decompose creating
polymeric free radicals. Unhindered, the radicals generate in-situ
formation of crosslinked networks in the polymer of sufficient
quantity to evidence the increase in molecular weight, Mz, and
Mooney viscosity.
Mooney Stabilizers
To address the issue of generated polymeric free radicals during
the bromine regenerative process, a free-radical stabilizer,
free-radical scavenger, or antioxidant, collectively referred to
herein as a "Mooney stabilizer" or "stabilizer", is incorporated
into the polymer or polymer slurry prior to the point of creation
of free radicals or creation of an in-situ cross-linked network.
The Mooney stabilizer may be oil-soluble or a water compatible
compound, with a preference for an oil-soluble compound including
but not limited to a hexane-soluble compound.
Suitable Mooney stabilizers include, but are not limited to,
sterically hindered nitroxyl ethers, sterically hindered nitroxyl
radicals, butylated hydroxytoluene (BHT), hydroxyhydrocinnamite,
thiodipropinoate, phosphites, and combinations thereof.
The sterically hindered nitroxyl ether, according to the present
invention, has, but is not limited to, the structure represented by
either the formula (I) or (II), where n is a number from 1 to 10
and R.sub.1 is propyl.
##STR00001##
The sterically hindered nitroxyl radical has, but is not limited
to, the structure represented by the formula (Ia), where n is a
number from 1 to 10.
##STR00002##
Commercially available examples of Mooney stabilizers that can be
added during the preparation of bromobutyl elastomers in the
present invention include, but are not limited to, TEMPO,
Tinuvin.TM. NOR 371, Irganox PS 800, Irganox 1035, Irganox 1010,
Irganox 1076, Irgaofs 168. TEMPO is a term generally used in the
art to refer to (2,2,6,6-tetramethylpiperidin-1-yl)oxy. The
sterically hindered nitroxyl radical tested in the invention is
TEMPO. Tinuvin.TM. NOR 371 is a high molecular weight hindered
amine NOR stabilizer, commercially available from BASF as a plastic
additive. The sterically hindered nitroxyl ether tested in the
invention is Tinuvin.TM. NOR 371. Irganox PS 800 is commercially
available from CIBA and is the trade name of didodecyl
3,3'-thiodipropionate. Irganox 1035 is commercially available from
CIBA/BASF and is the trade name of thiodiethylene bis
(3,5-di-tert-butyl-4-hydroxyhydrocinnamate). Irganox 1010 is
commercially available from BASF and is the trade name of
pentaerythritol
tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate). Irganox
1076 is commercially available from CIBA and is the trade name of
octadecyl-3-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionate. The
sterically hindered phenolics tested in the invention include BHT,
Irganox PS 800, and Irganox 1035. Irgafos 168 is commercially
available from BASF and is a general purpose phosphite. In
embodiments, other Mooney stabilizers may be added to the
bromobutyl-based elastomeric composition of the invention
including, but not limited to, light stabilizers and
UV-absorbers.
Referring to FIGS. 1 and 2, in an embodiment, the Mooney stabilizer
is added via cement stream C. In another embodiment, the Mooney
stabilizer is added to the bromination unit 10 via stream X2. In
another embodiment, the Mooney stabilizer is added to the stream F
via X3 before the effluent from the bromination unit 10 has been
neutralized by stream N. In another embodiment, the Mooney
stabilizer is added to the neutralization unit 20. In yet another
embodiment, Mooney stabilizer is added to the stream NF via X4
after the neutralization unit 20.
In an embodiment, the Mooney stabilizer may be added in more than
one location in the halogenation process, provided a portion of the
Mooney stabilizer is added prior to a step involving a significant
heat change. When the Mooney stabilizer is added before or during
neutralization, residency time in the process provides time for the
stabilizer to counter any oxidized structures and/or polymeric free
radical. The Mooney stabilizer may be added to the stream C, or to
the bromination unit 10, or to the bromination effluent F prior to
neutralization, or to unit 20 during neutralization, or after
neutralization NF, or to the extrusion drying unit 40, or the
devolatizer unit 50, and any combinations thereof.
In any embodiment, the total amount of Mooney stabilizer to be
added during the process of preparing the brominated elastomer is
greater than about 500 ppm, greater than about 800 ppm, greater
than about 1,000 ppm to less than about 2,000 ppm, to less than
about 5,000 ppm, or less than about 10,000 ppm, or is in any range
created by one of the above minimum amounts in combination with
either of the stated maximum amounts. The ppm weight basis is the
weight of the brominated polymer (whether in solution, slurry, or
recovered).
TEST METHOD AND EXAMPLES
Oven Aging Test
To mimic warehouse conditions and obtain the data of FIG. 3, the
polymer samples were subjected to an Oven Aging Test as described
herein Immediately after recovering the polymer samples from the
brominated elastomer slurry (i.e., stream P of FIG. 1 or 2) or
after storing the sample for not more than 90 days at about
25.degree. C., a sample is taken from a bale, cut into 2'' cubes
from the interior of the bale, wrapped in Chemfab 50-8 (Teflon
coated glass, 6 mil, 12'' by 36 yard roll), and double-wrapped with
aluminum foil. The foil wrapped samples aged at 80.degree. C. for
4-5 days in a conventional oven are expected to exhibit properties
similar to compositions in warehouse conditions for 1 year. The
foil wrapped samples aged at 80.degree. C. for 8-10 days in a
conventional oven are expected to exhibit properties similar to
compositions in warehouse conditions for 2-2.5 years. It is
appreciated that specific warehouse conditions can vary depending
on the geographic location of the warehouse and this test is only
an approximation for average warehouse conditions. During the oven
aging test, the foil wrapped samples were unwrapped and about
0.25'' was shaved from each side of the sample, resulting in an
aged sample suitable for testing. As evidenced in FIG. 3, samples
prepared by both conventional and known regenerative bromination
methods showed an increase in Mooney viscosity growth over
time.
Stabilizer Testing
Polymer cements of brominated isobutylene-isoprene were blended
with different Mooney stabilizers at different levels to determine
the effect of the stabilizers on the molecular weight stability
(i.e., control of Mooney viscosity growth) of the polymer. Samples
of cements were combined with the identified Mooney stabilizer,
removed from a hexane solvent, and formed into a film. The films
were aged for 24 hours in a nitrogen-purged oven at 90.degree. C.
The Mz of each sample were calculated before and after the oven
aging. Results are set forth below in Table 1.
As the regenerative process used to prepare the polymer cements
tested in Table 1 used hydrocarbon as a solvent, a selection of
stabilizers were tested in Table 1 so that the stabilizer remains
in the hydrocarbon phase during neutralization (the addition of
stream N in FIGS. 1 and 2) and reslurry steam stripping (the
addition of stream S in FIG. 1) step. It is expected that other
Mooney stabilizers mentioned herein would likewise reduce Mooney
growth and change in Mz. The Mooney stabilizers suitable for use in
the regenerative process of the invention include but are not
limited to those tested in Table 1.
TABLE-US-00001 TABLE 1 Mooney stabilizer ppm Mz % change None
(control) -- 43 Irganox PS 800 100 53 1,000 38 10,000 5 Irganox
1035 100 1 1,000 4.5 10,000 2.5 Butylated 100 9 Hydroxytoluene
1,000 5 10,000 5 TEMPO 100 -0.5 1000 -0.5 10,000 15 Tinuvin .TM.
100 0 NOR 371 1,000 11 10,000 16
The majority of stabilizers tested in Table 1 inhibited GPC Mz
change (and therefore Mooney viscosity growth), even at 100 ppm
levels. Irganox PS 800 showed unfavorably high Mooney growth at 100
ppm and 1,000 ppm levels, as compared to the control, but showed
substantial decrease in Mooney at 10,000 ppm levels. Surprisingly,
some stabilizers (such as TEMPO and Tinuvin.TM. NOR 371) showed
more favorable Mooney growth suppression at lower levels of 100 ppm
and 1,000 ppm levels, rather than at 10,000 ppm levels. Table 1
indicates that the amount and type of Mooney stabilizer can be
selected based on the required Mooney growth suppression of the
brominated elastomer.
Stabilization Trials
Polymer samples were prepared by conventional bromination and
regenerative bromination processes. In both of the processes, 400
ppm BHT was added prior to the steam stripping unit 30 at feed X4
and another 400 ppm BHT was added into unit 40 at feed X5. In one
run of the regenerative bromination process, an additional 800 ppm
BHT was injected into the system prior to neutralization (via X3 of
FIGS. 1 and 2) present in the system during neutralization. So the
conventional bromination produced samples and the first
regenerative bromination produced samples contained 800 ppm BHT and
the samples prepared via regenerative bromination with additional
BHT contained 1600 ppm BHT. All three types of samples had 1.3 wt %
of epoxidized soybean oil added to the polymers after
neturalization of the bromination effluent stream F.
The samples were oven aged for 9 months at 33.degree. C.; the
testing temperature selected to mimic maximum summer warehouse
conditions that may be experienced by the polymers. It should be
noted that as a constant temperature was maintained during testing,
potential minimum winter temperature warehouse conditions are not
represented in the data; one in the art would readily appreciate
cooler warehouse temperatures will reduce Mooney growth tendencies
of the polymer samples. Prior to oven aging the polymer samples
were prepared in the same manner as described above: the samples
were 2'' cubes obtained from the interior of a polymer bale,
wrapped in Chemfab 50-8, and double-wrapped with aluminum foil; the
samples remained so wrapped for the length of the oven aging
period. The Moony viscosity of each sample was measured at the
beginning of the testing period to establish a baseline Mooney
viscosity value against which a delta Mooney could be determined to
measure change; the actual Mooney values for each polymer sample
were not identical. Samples were removed at months end for nine
consecutive months and the Mooney viscosity was measured to
determine the change in value.
The change in the Mooney viscosity from the initial Mooney
viscosity value (i.e., the delta Mooney) as measured at the end of
each of the nine consecutive months is shown in FIG. 5 for the
samples. The conventional bromination process samples are
identified as "Pre-trial control, no additional BHT", the first
regenerative bromination process samples are identified as "Br
Regen control, no additional BHT" (these samples contained 800 ppm
BHT), and the second regenerative bromination process samples are
identified as "Br Regen, added .about.800 ppm BHT" (these samples
contained 1600 ppm BHT). As evident by the data in FIG. 5, all
three types of samples experienced Mooney viscosity growth, and as
expected samples prepared by the conventional bromination method
(Pre-trial control) experienced the least Mooney viscosity growth.
At nine months aging, the conventional bromination samples had an
average delta Mooney of about 10.1, the regenerative bromination
samples having 800 ppm BHT had an average delta Mooney of about
13.1, and the regenerative bromination samples having 1600 ppm BHT
had an average delta Mooney of about 11.3. In comparing the
regenerative bromination methods, when including an additional
amount of Mooney viscosity stabilizer during neturalization of the
brominated elastomer effluent, the Mooney viscosity growth wherein
the conventional bromination method is the baseline target for
Mooney value was surprisingly reduced by more than fifty percent
though the temperature of the system had not yet undergone a
significant temperature change. In other words, the Mooney
viscosity growth delta between the conventional control sample and
the "Br Regen, .about.800 ppm BHT" sample is less than fifty
percent of the delta between the conventional control samples and
"Br Regen control" sample. While the data in FIG. 5 is only for
nine months of simulated summer warehouse aging, based on
mathematically reasonable projections of the delta Mooney values,
the one year delta Mooney data for the 1600 ppm BHT regenerative
bromination sample should not exceed 15, and will likely not exceed
13, and for the 800 ppm BHT regenerative bromination control
sample, the one year delta Mooney data should not exceed 16, and
will likely not exceed 15.
In comparing the data of FIG. 3 (wherein 2 to 2.5 years warehouse
aging was imitated by accelerated high temperature aging) and FIG.
5, it can be seen that adding at least one portion of Mooney
stabilizer prior to the brominated polymer obtained via
regenerative processes undergoing a significant temperature change
reduces the delta Mooney of the aged brominated polymer in
comparison to brominated polymer obtained via conventional
halogenation methods. The addition of Moony stabilizer may be done
in a single process location or in multiple process locations.
While all the tested samples evaluated had an minimum amount of 800
ppm of BHT added prior to steam stripping, it is appreciated that
other ranges of Mooney stabilizer, as low as a total of 500 ppm,
may be suitable for injection in accordance with the present
invention. Furthermore, it is appreciated that other Mooney
stabilizers disclosed herein (in place of or in addition to BHT)
can be equally or more effective at Mooney growth suppression. It
is also appreciated that in addition to injecting a Mooney
stabilizer before and/or after neutralization via lines X3 or X4,
it is also suitable to add the Mooney stabilizer to cement via X1
or in the bromination unit 10 via X2, as depicted in FIGS. 1 and 2.
In an embodiment, the Mooney stabilizer is added to the devolatizer
unit 50 as depicted in FIG. 2.
Certain embodiments and features have been described using a set of
numerical upper limits and a set of numerical lower limits. It
should be appreciated that ranges from any lower limit to any upper
limit are contemplated unless otherwise indicated. Certain lower
limits, upper limits, and ranges appear in one or more claims
below. All numerical values are "about" or "approximately" the
indicated value, and take into account experimental error and
variations that would be expected by a person having ordinary skill
in the art.
To the extent a term used in a claim is not defined above, it
should be given the broadest definition persons in the pertinent
art have given that term as reflected in at least one printed
publication or issued patent. Furthermore, all patents, test
procedures, and other documents cited in this application are fully
incorporated by reference to the extent such disclosure is not
inconsistent with this application and for all jurisdictions in
which such incorporation is permitted.
While the foregoing is directed to embodiments of the present
invention, other further embodiments of the invention may be
devised without departing from the basic scope thereof, and the
scope thereof is determined by the embodiments that follow.
Specific Embodiments
The invention, accordingly, provides the following embodiments:
Paragraph A: A method of preparing a brominated elastomer, the
method comprising polymerizing a C.sub.4 to C.sub.7 isomonoolefin
and at least one monomer or polymerizable unit to obtain a C.sub.4
to C.sub.7 isomonoolefin derived elastomer; contacting the C.sub.4
to C.sub.7 isomonoolefin derived elastomer with a halogenating
agent and an emulsion in a bromination unit to form a brominated
elastomer effluent; neutralizing the brominated elastomer effluent
with a neutralizing agent and water to form a neutralized effluent;
volatizing a hydrocarbon solvent from the neutralized effluent to
form a brominated elastomer slurry; and recovering a brominated
elastomer from the brominated elastomer slurry wherein a Mooney
stabilizer is added to the process prior to volatizing of the
hydrocarbon solvent, the addition occurring before neutralization,
directly before neutralization, during neutralization, or following
neutralization before volatizing of the hydrocarbon solvent.
Paragraph B: The method of Paragraph A, wherein the Mooney
viscosity of the brominated elastomer, after recovering in step
(f), does not increase by more than about 17 Mooney units when
subject to or stored at 33.degree. C. for one year, or does not
increase by more than 15 Mooney units when subject to or stored at
33.degree. C. for one year, or does not increase by more than 13
Mooney units when subject to or stored at 33.degree. C. for one
year, or does not increase by more than 11.5 Mooney units when
subject to or stored at 33.degree. C. for nine months.
Paragraph C: The method of Paragraph A and/or B, wherein Mooney
stabilizer in amounts greater than about 500 ppm, or greater than
800 ppm, or greater than 1,000 ppm is added during the process of
preparing the brominated elastomer.
Paragraph D: The method of Paragraph A and optionally Paragraph B
and/or C, wherein the Mooney stabilizer is selected from at least
one of a sterically hindered nitroxyl ether, sterically hindered
nitroxyl radical, sterically hindered phenolics, phosphites, and
combinations thereof.
Paragraph E: An article made from the brominated elastomer
composition prepared by the method of Paragraph A and optionally
any one or any combination of Paragraphs B to D, wherein the
article is a tire innerliner or a tire bladder or is incorporated
as a layer into a tire, a bladder, a hose, a belt, pneumatic
spring, or vehicle body mount.
Paragraph F: The method of Paragraph A and optionally any one or
any combination of Paragraphs B to E, wherein the halogenating
agent is selected from at least one of molecular bromine, bromine
chloride, hydrogen bromide, and sodium bromide.
Paragraph G: The method of Paragraph A and optionally any one or
any combination of Paragraphs B to F, wherein the emulsion
comprises an oxidizing agent, water, solvent, and surfactant.
Paragraph H: The method of Paragraph G, wherein the oxidizing agent
is a material which contains oxygen selected from at least one of a
water soluble oxygen containing agent, hydrogen peroxide, organic
hydrogen peroxide, sodium chlorate, sodium bromate, sodium
hypochlorite, sodium hypobromite, oxides of nitrogen, ozone, urea
peroxidate, pertitanic perzirconic, perchromic, permolybdic,
pertungstic, perunanic, perboric, perphosphoric, perpyrophosphoric,
persulfates, perchloric, perchlorate, and combinations thereof.
Paragraph I: The method of Paragraph G, wherein the oxidizing agent
is a water soluble oxygen containing agent.
Paragraph J: The method of Paragraph G, wherein the solvent is
selected from at least one of pentane, hexane, heptane, mono-, di-,
or tri-halogenated C.sub.1 to C.sub.6 paraffinic hydrocarbon,
methyl chloride, and combinations thereof.
Paragraph K: The method of Paragraph A and optionally any one or
any combination of Paragraphs B to J, wherein the bromination unit
is a mixed flow stirred tank, a conventional stirred tank, a packed
tower, or a pipe.
Paragraph L: A method of preparing a brominated elastomer, the
method comprising polymerizing a C.sub.4 to C.sub.7 isomonoolefin
and at least one monomer or polymerizable unit to obtain a C.sub.4
to C.sub.7 isomonoolefin derived elastomer; adding a first portion
of a Mooney stabilizer to the C.sub.4 to C.sub.7 isomonoolefin
derived elastomer; contacting the C.sub.4 to C.sub.7 isomonoolefin
derived elastomer with a halogenating agent and an emulsion in a
bromination unit to form a brominated elastomer effluent, wherein
an optional portion of the Mooney stabilizer is added to the
bromination unit; adding an optional portion of the Mooney
stabilizer to the brominated elastomer effluent; neutralizing the
brominated elastomer effluent with a neutralizing agent and water
to form a neutralized effluent, wherein an optional portion of the
Mooney stabilizer is added to the neutralized effluent; volatizing
a hydrocarbon solvent from the neutralizing effluent to form a
brominated elastomer slurry; recovering a brominated elastomer from
the brominated elastomer slurry, wherein an optional portion of the
Mooney stabilizer is added to the brominated elastomer.
Paragraph M: The method of Paragraph L, wherein the Mooney
viscosity of the brominated elastomer, after recovering in step
(f), does not increase by more than about 15 Mooney units when
subject to 33.degree. C. for one year.
Paragraph N: The method of Paragraph L and/or M, wherein greater
than about 500 ppm of Mooney stabilizer is added during the process
of preparing the brominated elastomer.
Paragraph O: The method of Paragraph L and optionally M and/or N,
wherein the Mooney stabilizer is selected from at least one of a
sterically hindered nitroxyl ether, sterically hindered nitroxyl
radical, sterically hindered phenolics, phosphites, and
combinations thereof.
Paragraph P: An article made from the brominated elastomer
composition prepared by the method of Paragraph L and optionally
any one or any combination of Paragraphs M to O, wherein the
article is a tire innerliner or a tire bladder or is incorporated
as a layer into a tire, a bladder, a hose, a belt, pneumatic
spring, or vehicle body mount.
Paragraph Q: The method of Paragraph L and optionally any one or
any combination of Paragraphs M to P, wherein the halogenating
agent is selected from at least one of molecular bromine, bromine
chloride, hydrogen bromide, and sodium bromide.
Paragraph R: The method of Paragraph L and optionally any one or
any combination of Paragraphs M to Q, wherein the emulsion
comprises an oxidizing agent, water, solvent, and surfactant.
Paragraph S: The method of Paragraph R, wherein the oxidizing agent
is a material which contains oxygen selected from at least one of a
water soluble oxygen containing agent, hydrogen peroxide, organic
hydrogen peroxide, sodium chlorate, sodium bromate, sodium
hypochlorite, sodium hypobromite, oxides of nitrogen, ozone, urea
peroxidate, pertitanic perzirconic, perchromic, permolybdic,
pertungstic, perunanic, perboric, perphosphoric, perpyrophosphoric,
persulfates, perchloric, perchlorate, and combinations thereof.
Paragraph T: The method of Paragraph R, wherein the oxidizing agent
is a water soluble oxygen containing agent.
Paragraph U: The method of Paragraph R, wherein the solvent is
selected from at least one of pentane, hexane, heptane, mono-, di-,
or tri-halogenated C.sub.1 to C.sub.6 paraffinic hydrocarbon,
methyl chloride, and combinations thereof.
Paragraph V: The method of Paragraph L and optionally any one or
any combination of Paragraphs M to U, wherein the bromination unit
is a mixed flow stirred tank, a conventional stirred tank, a packed
tower, or a pipe.
Paragraph W: The method of any one or any combination of the above
Paragraphs wherein the at least one polymerizable unit is isoprene,
styrene, alkylstyrene, or a different C.sub.4 to C.sub.7
isomonoolefin.
Paragraph X: A brominated elastomer derived from a C.sub.4 to
C.sub.7 isomonoolefin and at least one polymerizable unit selected
from isoprene and alkylstyrene, wherein the Mooney viscosity of the
brominated elastomer does not increase by more than about 15 Mooney
units for one year at 33.degree. C.
Paragraph Y: A brominated elastomer prepared by any one or any
combination of Paragraphs A to K or prepared by any one or any
combination of Paragraphs L to W, or is the elastomer of Paragraph
X wherein the brominated elastomer contains 0.001 to 0.2 mol % of
allylic alcohol.
INDUSTRIAL APPLICABILITY
The inventive polymers can be used to make any number of articles.
In one embodiment, the article is selected from tire curing
bladders, tire innerliners, tire innertubes, and air sleeves. In
another embodiment, the article is a hose or a hose component in
multilayer hoses, such as those that contain polyamide as one of
the component layers. Other useful goods that can be made using
polymers of the invention include air spring bladders, seals,
molded goods, cable housing, rubber-based pharmaceutical stoppers,
and other articles disclosed in THE VANDERBILT RUBBER HANDBOOK, PP.
637-772 (Ohm, ed., R.T. Vanderbilt Company, Inc. 1990).
All priority documents, patents, publications, and patent
applications, test procedures (such as ASTM methods), and other
documents cited herein are fully incorporated by reference to the
extent such disclosure is not inconsistent with this invention and
for all jurisdictions in which such incorporation is permitted.
When numerical lower limits and numerical upper limits are listed
herein, ranges from any lower limit to any upper limit are
contemplated.
* * * * *